Determination of process contaminants 2- and 3-MCPD esters and glycidyl esters in palm-based glycerol by indirect analysis using GC-MS.

Esters of 2- and 3-monochloropropanediol (2-MCPDE, 3-MCPDE) and glycidol (GE) are regarded as process contaminants that are found in refined vegetable oils and oil-based foods. Since glycerol is produced during fat splitting, saponification and biodiesel production, it is important to have methods for determining contaminants that might be formed during these processes. Due to the use of glycerol as a food additive, data on the presence of compounds of toxicological concern, including 3-MCPD, are of interest. This study focuses on modifying the indirect analysis of 2-MCPDE, 3-MCPDE and GE using GC-MS based on the AOCS Official Method Cd 29a-13, validating the modified method, and quantifying 2-MCPDE, 3-MCPDE and GE in glycerol. The AOCS Cd 29a-13 method was modified at the initial stage of sample preparation in which the targeted esters were extracted from glycerol by vortex-assisted extraction before sample analysis. This modification was performed based on the polarity of all compounds involved. The calibration functions for all analytes were fitted to linear regression with R2 above 0.99. Limits of detection (LOD) 0.02, 0.01 and 0.02 mg kg-1 were obtained for 2-MCPDE, 3-MCPDE and GE, respectively. Spiked glycerol with 3-MCPDE and 2-MCPDE (0.25, 0.51 and 1.01 mg kg-1) and GE (0.58, 1.16 and 2.32 mg kg-1) were used for recovery and precision measurements. Recoveries of 100-108%, 101-103%, and 93-99% were obtained for 2-MCPDE, 3-MCPDE and GE, respectively. Acceptable precision levels with relative standard deviations ranged from 3.3% to 8.3% were obtained for repeatability and intermediate precision. The validated method was successfully applied for the analysis of the target compounds in refined glycerol from commercial plants, which showed that 2-MCPDE, 3-MCPDE and GE levels in the analysed samples were below the detection limit.

The occurrence of 3-monochloropropane-1,2-diol esters and glycidyl esters in vegetable oils during frying.

3-monochloropropane-1,2-diol esters (3-MCPDE) and glycidyl esters (GE) are processed-developed contaminants presence in vegetable oils after undergo refining process under excessive heat. Refined oils are extensively used in various frying applications, nevertheless, the reservation against their quality and safety aspects are of major concern to consumers and food industry. Realizing the importance to address these issues, this article deliberates an overview of published studies on the manifestation of 3-MCPDE and GE when vegetable oils undergo for frying process. With the modest number of published frying research associated to 3-MCPDE and GE, we confined our review from the perspectives of frying conditions, product properties, antioxidants and additives, pre-frying treatments and frying oil management. Simplicity of the frying process is often denied by the complexity of reactions occurred between oil and food which led to the development of unwanted contaminants. The behavior of 3-MCPDE and GE is closely related to physico-chemical characteristics of oils during frying. As such, relationships between 3-MCPDE and/or GE with frying quality indices - i.e. acidity in term of free fatty acid or acid value); secondary oxidation in term of p-anisidine value, total polar compounds and its fractions, and refractive index - were also discussed when oils were subjected under intermittent and continuous frying conditions.

In-house validation of accelerated solvent extraction-gas chromatography-mass spectrometry for the determination of bound 3- and 2-monochloropropanediols (MCPD) and glycidol in food products.

The study aimed to establish the detection method for bound 3-, 2-MCPD, and glycidol using accelerated solvent extraction (ASE) and gas chromatography mass spectrometry (GC-MS). The ASE was modified for reduced solvent volume and process time to extract lipid from the chocolate spread, infant formula, potato chips, and sweetened creamer. The solvent selected for ASE was a mixture of iso-hexane and acetone at 100°C with the lipid and analyte recovery ranging from 96.9% to 98.6% and 84.1% to 107.5%, respectively. The derivatisation of analytes was adopted from the AOCS method Cd29a-13 for GC-MS analysis. The results showed that the coefficient of determination (R2) of all analytes was >0.99. The limit of detection (LOD) was 0.1 mg kg-1 expressed in lipid basis for both bound 3- and 2-MCPD and 0.2 mg kg-1 expressed in lipid basis for bound glycidol. The limit of quantitation (LOQ) was 0.3 mg kg-1 expressed in lipid basis for both bound 3- and 2-MCPD and 0.6 mg kg-1 expressed in lipid basis for bound glycidol. A blank spiked with 3-monochloropropanediols fatty acid esters (MCPDE) and 2-MCPDE (0.3, 2.1, and 7.2 mg kg-1) and glycidol esters (0.6, 4.7, and 16.6 mg kg-1) were chosen for accuracy and precision tests. The recoveries were 91.7% to 105.9%. Both repeatability and within-laboratory reproducibility of the analysis were within the acceptable level of precision ranging from 1.7% to 16%. This is the first time that a full validation procedure extending to both accuracy and precision tests has been carried out for sweetened creamer and chocolate spread. Overall, the combined protocol of ASE and AOCS Cd29a-13 was successfully validated for both solid and liquid food samples with lipid content from 10% to 30%.

Verification and evaluation of monochloropropanediol (MCPD) esters and glycidyl esters in palm oil products of different regions in Malaysia.

This study was conducted to investigate on the effect of different sampling regions of palm-refined oils and fats on the 2- and 3-monochloropropanediol fatty acid esters (MCPDE) and glycidol fatty acid esters (GE) levels. The American Oil Chemists' Society (AOCS) Official Method Cd 29a-13 on the determination of MCPDE and GE in edible oils and fats by acid transesterification was successfully verified and optimised, with slight modification using 7890A Agilent GC system equipped with 5975C quadrupole detector. The determined limits of detection (LOD) for MCPDE were 0.02 mg kg-1 and 0.05 mg kg-1 for GE. The method performance has showed good recovery between 80% and 120% for all pertinent compounds with seven replicates assayed in three separate days. Round robin test with two European laboratories, i.e. Eurofins and SGS, has shown compliance results with those of the present study. Among the sampling regions, only one refinery located in the central region of Malaysia showed a significant increment of the MCPDE and GE levels after refining process. The GE level averaging at 2.5 mg kg-1 was slightly higher than that of 3-MCPDE averaging at 1.3 mg kg-1. Both esters were preferentially partitioned into the liquid phase rather than the solid phase after fractionation. However, the overall results exhibited no direct correlation between the esters content and the different sampling locations of the palm oil products in Malaysia. Analysis of total chlorine content also displayed significant variations between sampling locations which clearly show its effect on the chlorine content in the CPO samples.

Effect of Anti-Clouding Agent on the Fate of 3-Monochloropropane-1,2-Diol Esters and Glycidyl Esters in Palm Olein during Repeated Frying.

Issues on 3-monochloropropane-diol-1,2-diol (MCPD) esters and glycidyl esters in refined oil have gained much attention when these heat-induced contaminants are associated with health implications. Oil that undergoes the frying process could influence the fates of 3-MCPD esters and glycidyl esters, especially with the addition of an anti-clouding agent. In this study, we investigated the effect of polyglycerol fatty acid esters (PGE) on the transients of 3-MCPD esters and glycidyl esters in palm olein (POo) during intermittent frying. Thermal resistance of POo fortified with PGE (0.1% to 0.4%) was assessed for 8 h of daily frying operations at 180 °C across five consecutive days. The addition of PGE decelerated the reduction of 3-MCPD esters and glycidyl esters with the progression of frying. The presence of these compounds coincided with the amount of oil taken up by the fried product. The inclusion of PGE in POo also induced higher augmentation of polar compound fractions, i.e., oxidised triacylglycerols (OxTAG) and polymerised triacylglycerols (PTAG), but gave comparable free fatty acid (FFA), p-anisidine value (AnV), total chloride and fatty acid composition (FAC) with control oil (POo). The results also showed that the presence of chloride in POo did not onset further formation of 3-MCPD esters and glycidyl esters throughout the frying period. As the behaviours of 3-MCPD esters and glycidyl esters were affected by PGE, only a sufficient amount should be added into POo to ensure oil clarity at a realistic period.

Feasibility of Continuous Frying System to Improve the Quality Indices of Palm Olein for the Production of Extruded Product.

Comparative frying studies on the processing of extruded product were conducted under intermittent and continuous frying conditions using two separate frying systems, i.e batch and pilot scale continuous fryers, respectively. Thermal resistance of palm olein were assessed for a total of 5 days of frying operation at 155°C - the unconventional frying temperature gave the product moisture content of 3% after intermittent and continuous frying for 2.5 min and 2 min, respectively. The formation of free fatty acid in palm olein in the case of intermittent frying was more than 2-fold higher compared to its counterpart (0.66%). Smoke point inversely evolved with oil acidity: the value dropped progressively from 215 to 177°C and from 219 to 188°C when extruded product was intermittently and continuously fried, respectively. In the light of induction period, repeated frying exhibited a gradual decrease in the value after 5 days of frying (12.2 h). Interestingly, continuous frying gave somewhat similar induction period, as demonstrated by fresh palm olein, across frying time. Frying at lower temperature, to some extent, provides opportunity for palm olein to retain 74% of its initial vitamin E during continuous frying. This benefit, however, is somehow denied when extruded product was processed under intermittent frying conditions--only 27% of vitamin E was remained at the end of frying session. Regardless of frying protocols, transient in polar compounds was minimal and hence comparable. The colour in the case of continuous frying appeared to be darker due to higher degree of oil utilisation for frying. The data obtained will provide useful information for food processors on how palm olein behaves when frying is undertaken under different frying protocols.

On the possibility of nonfat frying using molten glucose.

Fried products impose a health concerns due to considerable amount of oil they contain. Production of snack foods with minimal oil content and good management of oil during frying to minimize the production of toxic compounds continue to be challenging aims. This paper aims to investigate the possibility of producing a fat-free food snack by replacing frying oil with a nonfat medium. Glucose was melted and its temperature was then brought to 185 °C and used to fry potato strips, to obtain a product referred here as glucose fries. The resulting product was compared with French fries prepared conventionally under conditions that resulted in similar final moisture content. The resulting products were also examined for crust formation, texture parameters, color development and glucose content. Stereo microscope images showed that similar crusts were formed in the glucose fries and French fries. Texture parameters were found to be similar for both products at 5 and 2 mm penetration depth. The maximum hardness at 2 mm penetration depth was also similar for both products, but different from cooked potato. The color development that characterized French fries was also observed in glucose fries. The glucose content in glucose fries was found to be twice the content of French fries, which is to be expected because glucose absorbed or adhered to the surface. In conclusion, glucose fries, with similar texture and color characteristics to that of French fries, can be prepared by using a nonfat frying medium.

Physico-chemical changes occurring in oil when atmospheric frying is combined with post-frying vacuum application.

The aim of this study was to investigate the effect of atmospheric frying followed by drainage under vacuum on the stability of oil, compared to similar frying with drainage at atmospheric pressure. Changes in the oil were assessed by the free fatty acid (FFA) content, p-anisidine value (AnV), colour, viscosity, fatty acid profile and concentration of tocols. The rate of FFA formation in the case of vacuum drainage was found to be about half that of atmospheric drainage. Oil deterioration by oxidation and polymerisation was also reduced by the use of vacuum drainage. The AnV of the oil after vacuum drainage was lower by about 12%, the total colour difference was improved by 14% and viscosity was slightly reduced after 5 days of frying, compared to the values for oil that had been drained at atmospheric pressure. There was a reduction in the loss of polyunsaturated fatty acids in the case of vacuum drainage after 5 days of frying but differences in retention of tocols were only evident in the first two days of frying.